CN102443330A - Coating material and its preparation method - Google Patents

Abstract

A coating material is prepared from a resin matrix including a nano-modifier, an acrylic resin, and a silicone resin; wherein the nano-modifier adopts polyhedral oligomeric silsesquioxane POSS containing hydroxyl groups. The nano-modifier POSS of the present invention is uniformly dispersed in the resin matrix at the molecular level (see Figures 1, 2, and 3). The interaction between POSS and the resin collective is strong, which significantly improves the performance of the coating, especially the coating The gloss, transparency, hardness, flexibility, impact strength and artificial accelerated aging resistance time of the coating are greatly improved; the pencil hardness of the coating is 3-6H, the gloss (Gloss20o) is 95-96, and the flexibility is 1-3mm. The impact strength is 60-80kg/cm, and the artificial accelerated aging resistance time is ≥1000 hours. It can be widely used in the surface coating of cars, metals, plastics, buildings, stone, wood, leather, textiles, etc.

Description

A kind of coating material and preparation method thereof

technical field

The invention relates to a coating material, in particular to a nano-modified organic-inorganic hybrid coating material and a preparation method thereof, belonging to the field of new materials. the

Background technique

Coating material is a material coated on the surface of other objects to decorate, protect or give objects new functions. Traditional coating materials include organic coatings and inorganic coatings, both of which have their own advantages and disadvantages. With the rapid development of science and technology, people have higher and higher requirements for coating materials, and it is difficult for materials prepared with a single composition to meet various needs at the same time. Organic-inorganic hybrid coating materials formed by combining organic polymers and inorganic compounds at the molecular or nanoscale scale are expected to greatly improve the performance of one-component coating materials. the

Organic-inorganic hybrid coating materials are the fourth generation of coating materials after single-component coating materials, composite coating materials and gradient coating materials, which have aroused great interest in the scientific and industrial circles. For example, the patent US5670257 introduced a method of blending polysiloxane in acrylic resin to prepare organic-inorganic hybrid resin particles for use on the surface of liquid crystal displays. The patent US6288198 introduces a hybrid coating prepared by reacting isocyanate and aminosilane, which is used for surface coating of metals and plastics. Patent US5013608 introduces a preparation method of siloxane/silicon dioxide hybrid coating, and the prepared hybrid coating material has the function of high wear resistance and absorbing ultraviolet rays. the

Acrylic resin is widely used in automobiles, motorcycles, electric vehicles, home appliances, instruments, construction, office products and other metal products, plastic parts, wood products, paper products due to its excellent gloss, transparency, weather resistance, etc. Wait for the top coat. Traditional acrylic coating materials are mostly made of acrylic resin containing functional groups and polyisocyanate or amino resin cross-linked and cured. Polyisocyanate is used as curing agent, and the residual free HDI, TDI, MDI, and TPDI have strong Irritation and toxicity, using amino resin as curing agent requires high temperature baking and curing, and whether polyisocyanate is used as curing agent or amino resin is used as curing agent, the coating's weather resistance, temperature resistance, oxidation resistance, Abrasion resistance etc. are not very ideal, and all need to be further improved. the

The most reported in the literature is the method of using silicone-modified acrylic coatings. For example, JP89-60618 uses octamethylcyclotetrasiloxane and methylvinylcyclosiloxane to make silicon intermediates, and then mixes them with acrylic acid monolayers. The method of body copolymerization is used to prepare silicone modified acrylic resin. JP95-196975 uses 3-methacrylic trimethoxysilane to copolymerize with acrylic acid monomers in a solvent to make a silicone-modified acrylic resin. The above-mentioned organosilicon-modified acrylate resins have a common feature that organosilicon functional groups are introduced into the main chain and side chain of their macromolecules, and the bond energy of the Si-O covalent bond is 25Kcal/mol higher than the C-C bond energy, which is greatly improved. Improved heat and light stability of acrylic resins. In particular, the prepared coating material has the characteristics of high adhesion, stain resistance, water resistance, heat resistance and aging resistance. However, the production process of silicon intermediates is strict, and the storage stability of silicone-modified acrylate resins synthesized directly from silicon monomers containing unsaturated double bonds is unstable and prone to gelation. the

Nanomaterials refer to materials with at least one dimension in the nanoscale range in the three-dimensional scale. Because their scale is between atoms and macroscopic crystals, they show small size effects, surface and interface effects, quantum effects, etc., and here Various macroscopic crystals derived from the basis do not have the characteristics. Due to the superiority of nanomaterials, adding them as fillers to the resin system can greatly improve the performance of coating materials. The currently used nanoparticles mainly include nano-silica system, organically modified nano-clay system, nano-titanium dioxide system, etc. For example, Chinese patent ZL02111699.7 reports a preparation method of a high-scratch-resistant nano-composite polyurethane coating. Nano-composite acrylate polyurethane coatings are obtained by modifying nanoparticles such as nano-silica and calcium carbonate in situ or by blending. layer, scratch resistance can be increased by more than 25%; Japanese patent JP2004323634 reported a nano-modified acrylic composition and its preparation method, using inorganic nanoparticles, thermoplastic acrylic resin, thermosetting acrylic resin prepared nano-modified acrylic resin combination It has high transparency, high elastic modulus, etc., and can be used for interior and exterior decoration of automobiles. the

The filling of the above-mentioned nanoparticles has a certain effect on improving the hardness and wear resistance of the polymer, but it has the following disadvantages: (1) the nano-inorganic particles are agglomerated due to incompatibility with the matrix, although the nanoparticles are surface-modified Or coating is beneficial to reduce agglomeration, but the process is complicated, industrialization is difficult, and the surface energy of nanoparticles is large, and the tendency of agglomeration is unavoidable; (2) the addition of inorganic nanoparticles is often accompanied by a decrease in curing speed; (3) Nano The agglomeration of particles becomes the source of collective defects, and the impact strength decreases from time to time. Therefore, how to improve the dispersion performance of inorganic particles on the basis of nano-organic-inorganic hybridization without reducing the mechanical and kinetic properties has become the key to the preparation of high-performance coating materials. the

Polyhedral oligomeric silsesquioxane (POSS) is a kind of polymer reinforcement material that has received extensive attention internationally in recent years. POSS monomer is a kind of ring-shaped nanoscale cage molecule connected by Si-O as the skeleton. It is an organic/inorganic hybrid material at the complete molecular level. The typical molecular formula is (RSiO _1.5 ) or R ₇ X(SiO _1.5 ) _8. The core is a cage-type inorganic skeleton composed of silicon and oxygen. The fixed-point Si connects the group R extending to the space. R is H, alkyl, alkenyl, aryl, aralkenyl or derivatives of these groups, X as an active functional group. Its molecular structure analysis diagram is shown in the figure below. The POSS structure mainly has the following two characteristics: (1) The chemical composition is RSiO _1.5 , which is a hybrid intermediate between R ₂ SiO and SiO ₂ . Among them, the inorganic scaffold structure composed of Si and O endows the hybrid material with good heat resistance and mechanical properties; (2) POSS molecules are nanometer-sized, in the range of 1-3nm, with multifunctional characteristics and inorganic Si-O structure. Externally connected alkane substituents or active reactive groups, organic groups can improve the compatibility between POSS and polymers, and reactive groups can realize chemical bonding between POSS and polymers.

Analysis of POSS molecular structure

POSS has many advantages over traditional fillers. Traditional fillers are relatively large in size (>50nm) and are usually used to reinforce polymers macroscopically. Calculation shows that when the size of the filler is less than 50nm, it will not easily settle and can strengthen the polymer system more effectively. Therefore, traditional fillers cannot control the movement of polymer segments at the molecular level, especially the mismatch of chemical potentials (such as solubility, compatibility, etc.) between hydrocarbon-based polymers and inorganic fillers leads to unevenness. POSS is easily soluble in general polymers, which solves the long-standing problem of poor dispersion of traditional fillers. The POSS structure can be easily functionalized, has good compatibility with the polymer, and basically does not change the processing conditions of the polymer, so the modification synthesis technology of the POSS molecule allows the multifunctional substituent POSS cage structure produced, which finely tune the relationship between POSS molecules and polymer chains, thus providing a means to control the mechanical and rheological properties. the

Contents of the invention

The purpose of the present invention is to provide a coating material with excellent comprehensive performance. the

Another object of the present invention is to provide a preparation method of the above-mentioned coating material, which is simple and very suitable for industrial scale production. the

The purpose of the present invention is achieved through the following technical measures:

A coating material, characterized in that: the coating material is made from a resin matrix comprising a nano-modifier, an acrylic resin, and a silicone resin; wherein the nano-modifier adopts polyhedral oligomerization Silsesquioxane POSS. the

In order to make the above-mentioned nano-modifier have better dispersibility in the above-mentioned resin matrix, the above-mentioned nano-modifier preferably adopts trisilanol isobutyl silsesquioxane (TriSilanolIsobutyl-POSS), trisilanol phenyl silsesquioxane alkane (TriSilanolPheny-POSS) or a silanol isobutyl silsesquioxane (MonoSilanolIsobutyl-POSS). the

Specifically, trisilanol isobutylsilsesquioxane (1,3,5,7,9,11,14-Heptaisobutyltricyclo[7.3.3.1(5,11)]heptasiloxane-endo-3,7,14- triol, referred to as TriSilanolIsobutyl POSS): product number SO1450, molecular formula C ₂₈ H ₆₆ O ₁₂ Si ₇ , molecular weight 791.42, and the structure is as follows:

Trisilanol phenylsilsesquioxane (1,3,5,7,9,11,14-Heptaphenyltricyclo[7.3.3.1(5,110)]heptasiloxane-endo-3,7,14-trio, referred to as TriSilanolPhenyl POSS): product number SO1458, molecular formula C ₄₂ H ₃₈ O ₁₂ Si ₇ , molecular weight 931.34, structure as follows:

Monosilanol isobutyl silsesquioxane (MonoSilanolIsobutyl-POSS for short): product number SO1445, molecular formula C ₂₈ H ₆₄ O ₁₃ Si ₈ , molecular weight 833.48, soluble in tetrahydrofuran, chloroform, n-heptane, insoluble in acetonitrile, white powder. Additive for surface modifiers, thermoplastic or thermosetting resins. The structure is as follows:

In order to further improve the dispersibility of the above-mentioned nano-modifier in the above-mentioned resin matrix, the amount of the above-mentioned nano-modifier is preferably 1-30 wt% of the raw material, in terms of mass percentage. the

In order to obtain a coating material with better comprehensive performance, the coating material of the present invention is the above-mentioned nano-modifier with a mass percentage content of 1 to 30 wt%, 40 to 98 wt% of acrylic resin, and 0 to 20 wt% of silicone resin. , 0-40wt% of solvent, 0-15wt% of pigment and filler and 0-7wt% of auxiliary agent are the nano-modified organic-inorganic hybrid coating material prepared as raw materials. the

Further preferably, the above-mentioned acrylic resin is an acrylic resin containing carboxyl, hydroxyl, epoxy or amide functional groups, and the solid content of the resin is 30 to 80 wt %; more preferably, the above-mentioned acrylic resin is carboxyl acrylic resin, hydroxyl acrylic resin , epoxy acrylic resin, alkoxy acrylic resin, amido acrylic resin, any two or any three components. the

Preferably, the aforementioned silicone resin is methyl silicone resin, methylphenyl silicone resin or MQ silicone resin. the

Specifically, the above-mentioned solvents can also be conventional solvents, such as hydrocarbon solvents, petroleum solvents, alcohol solvents, ester solvents, ketone solvents, ether solvents, and any 1 to 6 of them, such as ethanol, butyl Alcohol, isopropanol, acetone, methyl amyl ketone, acetylacetone, butyl acetate, ethyl butyrate, mineral spirits, xylene, etc. The above-mentioned pigments and fillers can also use conventional pigments and fillers, such as titanium dioxide, zinc oxide, iron oxide, aluminum oxide, pearlescent pigments, aluminum powder, silver powder, aluminum silicate, talcum powder, barium sulfate, etc., and any 1 to 5 of them can be used . The above-mentioned additives can be added with conventional additives, such as dispersants, wetting agents, defoamers, and leveling agents. the

In order to further improve the dispersion effect and the stability of pigments and fillers, the amount of dispersant added to the above-mentioned additives is 0.1-3wt% of the formulation amount; the type can be selected from 731A sodium salt dispersant, DP-19 dispersant, H-100 dispersant, One of the SN5027 dispersants. the

The active groups contained in the above-mentioned wetting agent are directional adsorbed on the surface of the pigment particles, which can increase the affinity between the coating substrate and the pigment, reduce the surface tension of the coating, and accelerate the penetration of the coating substrate into the pores between the pigment aggregate particles Among them, reduce energy consumption and improve efficiency, thereby reducing the overall cost of the formula; the above wetting agent can be added to one of X-405 wetting agent, NP-9 wetting agent, W-18, W-19 wetting agent species, and its addition amount is 0.1-5wt% of the formulation amount. the

The above-mentioned defoamers can effectively eliminate the bubbles generated during the production and construction of semi-finished varnishes, making the coating film smooth and smooth; for example, you can choose 013 defoamers, A10, A36 defoamers, SN154 defoamers, A kind of, its adding amount is 0.1～5wt% of formula quantity. the

The above-mentioned leveling agent can improve the leveling property of the coating film, increase the gloss, prevent shrinkage, fish eyes, orange peel and other phenomena, improve the scratch resistance of the coating film, and endow the substrate with good wetting properties , the addition amount is 0.1%~2wt%, for example, you can choose BYK-333 leveling agent, F40 leveling agent, RM-2020 leveling agent, RM-8 leveling agent, BD-3033 leveling agent, CA-400 water-based One of the pure leveling agents. the

The preferred additives are 731A sodium salt dispersant, X-405 wetting agent, 013 defoamer and BYK-333 leveling agent. the

More specifically, the coating material of the present invention is 10wt% trisilanol phenyl silsesquioxane, 63wt% epoxy acrylic resin, 2wt% methylphenyl silicone resin, 21wt% of isopropanol, 3wt% of alumina and 0.5wt% of 731A sodium salt dispersant, 0.2wt% of X-405 wetting agent, 0.2wt% of 013 defoamer, 0.1wt% of BYK-333 flow The leveling agent is used as a raw material to prepare a nano-modified organic-inorganic hybrid coating material. the

The preparation method of the above-mentioned coating material is characterized in that: in the reaction kettle, add the above-mentioned solvents, additives, pigments and fillers, stir at a speed of 1000-3000rpm for 0.5-1 hour, and then add the above-mentioned acrylic resin and silicone resin , stir evenly, add the above-mentioned nano-modifier, and stir at 300-2000rpm for 0.5-3 hours to obtain a nano-modified organic-inorganic hybrid coating material, and then the coating film is heated and cured in the range of 20-150 for 0.5 After ~24 hours, a nano-modified organic-inorganic hybrid coating is obtained. the

More preferably, the above added solvents, additives, pigments and fillers are stirred at 2200rpm for 0.8 hours; the above added acrylic resin, silicone resin and nano-modifier are stirred at 1400rpm for 0.5 hours. the

The present invention has the following beneficial effects:

The nano-modifier POSS of the present invention is uniformly dispersed in the resin matrix at the molecular level (see Fig. The gloss, transparency, hardness, flexibility, impact strength and artificial accelerated aging resistance time of the coating are greatly improved; the pencil hardness of the coating is 3H~6H, the gloss (Gloss 20°) is 95~96, and the flexibility is 1mm~ 3mm, impact strength 60kg/cm～80kg/cm, artificial accelerated aging resistance time ≥ 1000 hours (the coating gloss is measured according to GB1743-89 "Paint Film Gloss Measurement Method", and the coating pencil hardness is measured according to GB6739-1996 "Coating Film Hardness Pencil Test Method", the coating flexibility is measured according to GB1731-79 "Paint Film Flexibility Test Method", the impact strength of the coating is measured according to the "Paint Film Impact Resistance Test Method" stipulated in the GB1732 standard, and the artificial coating Accelerated aging resistance time is determined according to GB1865-97 "Determination of Paint Film Aging (Artificial Acceleration)"). the

The nano-modified organic-inorganic hybrid coating material prepared by the invention can be widely used in the surface coating of cars, metals, plastics, buildings, stone materials, wood, leather, textiles and the like. the

Description of drawings

Fig. 1 is the TEM image that accounts for the TriSilanolIsobutyl-POSS that 10wt% of raw material total amount is dispersed in acrylic resin and organosilicon resin matrix;

Fig. 2 is the TEM image that accounts for the TriSilanolPhenyl-POSS that 10wt% of raw material total amount is dispersed in acrylic resin and organosilicon resin matrix;

Fig. 3 is a TEM image of MonoSilanolIsobutyl-POSS, which accounts for 10 wt% of the total amount of raw materials, dispersed in acrylic resin and silicone resin matrix. the

In the figure, the black area represents POSS, and the white area represents the composite resin base of acrylic and silicone. It can be seen from Figures 1-3 that silanol-based POSS has a uniform nano-scale dispersion in the resin. Among them, the dispersion size of TriSilanolPhenyl-POSS in the resin is in the range of 5-20nm, and that of TriSilanolIsobutyl-POSS and MonoSilanolIsobutyl-POSS The dispersion size is in the range of 5-15nm. It can be seen that POSS has good dispersion in the resin matrix. the

The carried out transmission electron microscope analysis (TEM) adopts the Tecnai20 transmission electron microscope of American FEI company, and the accelerating voltage is 200kv. The samples were frozen and ultra-thin sectioned with a frozen ultra-thin microtome from LEICA Company, and the slice thickness was about 50-100 nm. the

Detailed ways

Embodiment 1: the prescription 1 of nano-modified organic-inorganic hybrid coating material is as follows:

In the reaction kettle, add 100 grams of xylene, 50 grams of carboxylated acrylic resin with a solid content of 50%, 80 grams of alkoxyacrylic resin with a solid content of 30%, 100 grams of methyl silicone resin with a solid content of 30%, and 0.6 grams of 731A sodium salt Powder, 0.6 g of X-405 wetting agent, 0.1 g of 013 defoamer, 0.2 g of BYK-333 leveling agent, slowly add 2 g of nano-modifier TriSilanolIsobutyl-POSS at 1000 rpm, within 5 to 10 minutes After the addition, continue to stir for 20-40 minutes, coat the film, and cure at 80° C. for 1 hour to obtain a nano-modified organic-inorganic hybrid coating material. the

The pencil hardness of the coating is 3H, the gloss (Gloss 20°) is 95, the flexibility is 1mm, the impact strength is 60kg/cm, and the artificial accelerated aging resistance time is ≥1000 hours. Among them, the coating gloss is measured according to GB1743-89 "Determination of Paint Film Gloss", the coating pencil hardness is measured according to GB6739-1996 "Pencil Measurement of Coating Film Hardness", and the coating flexibility is measured according to GB1731-79 "Determination of Paint Film Flexibility" The impact strength of the coating is measured according to the "Measurement Method for Impact Resistance of Paint Film" stipulated in the GB1732 standard, and the artificial accelerated aging resistance time of the coating is measured according to the GB1865-97 "Determination Method for Paint Film Aging (Artificial Acceleration)" Determination. the

Embodiment 2: the prescription 2 of nano-modified organic-inorganic hybrid coating material is as follows:

In the reaction kettle, add 45 grams of acetone, 25 grams of butyl acetate, 5 grams of isopropanol, 12 grams of titanium dioxide, 10 grams of aluminum powder, 0.6 grams of DP-19 dispersant, 0.6 grams of NP-9 wetting agent, 1.3 Gram A36 defoamer, 0.5 gram RM-2020 leveling agent, high-speed stirring 0.8 hour under 2200rpm rotating speed, then add 20 grams of epoxy acrylic resin of solid content 50%, 100 grams of solid content 50% hydroxyl acrylic resin, in Slowly add 12 grams of TriSilanolIsobutyl-POSS at 1400rpm, finish adding within 30 minutes, continue stirring for 30 minutes, coat the film, and cure at 90°C for 0.5 hours to obtain a nano-modified organic-inorganic hybrid coating material. the

The hardness of the coated pencil is 4H, the flexibility is 1mm, the impact strength is 60kg/cm, and the artificial accelerated aging resistance time is ≥1000 hours. The testing standard of performance is with embodiment 1. the

Embodiment 3: the prescription 3 of nano-modified organic-inorganic hybrid coating material is as follows:

In the reaction kettle, add 20 grams of methyl amyl ketone, 5 grams of 200# solvent oil, 7 grams of titanium dioxide, 5 grams of barium sulfate, 2 grams of iron oxide, 0.6 grams of SN5027 dispersant, 0.6 grams of W-18, 1.3 grams SN154 defoamer, 0.5 g of RM-8 leveling agent, high-speed stirring at 3000 rpm for 30 minutes, then add 35 g of solid content 60% amido acrylic resin, 50 g of solid content of 70% hydroxy acrylic resin, 10 g of solid content 30% methyl silicone resin, slowly add 24 grams of TriSilanolIsobutyl-POSS at 500rpm, finish adding within 30 minutes, continue to stir for 60 minutes, coat the film, cure at 50°C for 12 hours, and obtain nano-modified organic-inorganic hybrid coating material. the

Coating pencil hardness 5H, flexibility 1mm, impact strength 60kg/cm, artificial accelerated aging resistance time ≥ 1000 hours. the

Embodiment 4: the prescription 4 of nano-modified organic-inorganic hybrid coating material is as follows:

In the reaction kettle, add the above-mentioned additives and mix well, then add 80 grams of hydroxyacrylic resin with a solid content of 60%, and 10 grams of methyl silicone resin with a solid content of 50%, slowly add 40 grams of TriSilanolIsobutyl-POSS at 1000 rpm, at 30 The addition is completed within ~60 minutes, and the stirring is continued for 30 minutes, and the coating film is cured at 70°C for 1 hour to obtain a nano-modified organic-inorganic hybrid coating material. the

Coating gloss (Gloss 20°) 96, pencil hardness 5H, flexibility 1mm, impact strength 60kg/cm, artificial accelerated aging resistance time ≥ 1000 hours. the

Embodiment 5-9 prepares the coating material of the present invention according to the following materials, and the rest are the same as embodiment 1. the

The above-mentioned solvents can be conventional solvents, such as hydrocarbon solvents, petroleum solvents, alcohol solvents, ester solvents, ketone solvents, ether solvents, and any 1 to 6 of them, such as ethanol, butanol, isopropanol , acetone, methyl amyl ketone, acetylacetone, butyl acetate, ethyl butyrate, solvent naphtha, xylene, etc. The above-mentioned pigments and fillers can be conventional pigments and fillers, such as titanium dioxide, zinc oxide, iron oxide, aluminum oxide, pearlescent pigments, aluminum powder, silver powder, aluminum silicate, talcum powder, barium sulfate, etc., and any 1 to 5 of them can be used. The above-mentioned additives can be added with conventional additives, such as dispersants, wetting agents, defoamers, and leveling agents. Among them, the dispersant can choose one of 731A sodium salt dispersant, DP-19 dispersant, H-100 dispersant, and SN5027 dispersant. Wetting agent can add one of X-405 wetting agent, NP-9 wetting agent, W-18, W-19 wetting agent. Defoamer can choose one of 013 defoamer, A10, A36 defoamer, SN154 defoamer, 090 defoamer. Leveling agent can choose one of F40 leveling agent, RM-2020 leveling agent, RM-8 leveling agent, BD-3033 leveling agent, BYK-333 leveling agent, CA-400 water-based pure leveling agent . the

The coating material prepared above has a pencil hardness of 3H to 6H, a gloss (Gloss 20°) of 95 to 96, a flexibility of 1mm to 3mm, an impact strength of 60kg/cm to 80kg/cm, and an artificial accelerated aging resistance time of ≥ 1000 hours (where the coating The coating gloss is measured according to GB1743-89 "Determination of Paint Film Gloss", the coating pencil hardness is measured according to GB6739-1996 "Pencil Test of Coating Film Hardness", and the coating flexibility is measured according to GB1731-79 "Determination of Paint Film Flexibility" The impact strength of the coating is measured according to the "Determination of Impact Resistance of Paint Film" stipulated in the GB1732 standard, and the artificial accelerated aging resistance time of the coating is measured according to GB1865-97 "Determination of Paint Film Aging (Artificial Acceleration)"). It can be widely used in the surface finishing of cars, metals, plastics, buildings, stone, wood, leather, textiles, etc. the

Claims (10)

1. coated material is characterized in that: said coated material is to be that raw material makes with the resin matrix that comprises nano modifier and vinyl resin, silicone resin; Wherein nano modifier adopts the polyhedral oligomeric silsesquioxane POSS that contains hydroxyl.

2. coated material as claimed in claim 1 is characterized in that: said nano modifier preferably adopts three silanol isobutyl-silsesquioxanes, three silanol phenyl silsesquioxanes or a silanol isobutyl-silsesquioxane.

3. according to claim 1 or claim 2 coated material, it is characterized in that: the consumption of said nano modifier is the 1 ~ 30wt% that accounts for raw material, in the quality percentage composition.

4. according to claim 1 or claim 2 coated material is characterized in that: it is to be that the said nano modifier of 1 ~ 30wt%, the vinyl resin of 40 ~ 98 wt%, the silicone resin of 0 ~ 20 wt%, the solvent of 0 ~ 40wt%, the color stuffing of 0 ~ 15 wt% and the auxiliary agent of 0 ~ 7 wt% are that raw material makes with the quality percentage composition.

5. like claim 1 or 2 described coated materials, it is characterized in that: described vinyl resin is the vinyl resin that contains carboxyl, hydroxyl, epoxy group(ing) or carboxamido-group functional group, and the solid content of resin is 30 ~ 80wt%; More preferably, said vinyl resin is a kind of, any two kinds or any three kinds of components composition in carboxyl acrylic resin, Hydroxylated acrylic resin, epoxy group(ing) vinyl resin, alkoxy propone acid resin, the carboxamido-group vinyl resin.

6. coated material as claimed in claim 4 is characterized in that: said vinyl resin is a kind of, any two kinds or any three kinds of components composition in carboxyl acrylic resin, Hydroxylated acrylic resin, epoxy group(ing) vinyl resin, alkoxy propone acid resin, the carboxamido-group vinyl resin.

7. like claim 1,2,4 or 6 described coated materials, it is characterized in that: said silicone resin is methyl silicon resin, methyl phenyl silicone resin or MQ silicone resin.

8. coated material as claimed in claim 1 is characterized in that: it is to be the three silanol phenyl silsesquioxanes of 10wt%, the epoxy group(ing) vinyl resin of 63wt%, the methyl phenyl silicone resin of 2wt%, the Virahol of 21 wt%, the aluminum oxide of 3wt% and the 731A sodium salt dispersion agent of 0.5 wt%, the X-405 wetting agent of 0.2 wt%, 013 skimmer of 0.2wt%, the BYK of 0.1 wt% with the quality percentage composition -333 flow agents are that raw material makes.

9. like the preparation method of each said coated material of claim 1-8, it is characterized in that: in reaction kettle, add above-mentioned solvent, auxiliary agent, color stuffing; Under 1000 ~ 3000 rpm rotating speeds, stirred 0.5 ~ 1 hour; Add above-mentioned vinyl resin, silicone resin again, stir, add above-mentioned nano modifier; Under 300 ~ 2000 rpm rotating speeds, stirred 0.5 ~ 3 hour; Promptly get the nano modification organic-inorganic hybridized coatings, film then, promptly get nano modification hybrid inorganic-organic coating 20 ~ 150 scope internal heating curings 0.5 ~ 24 hour.

10. preparation method as claimed in claim 9 is characterized in that: said solvent, auxiliary agent, color stuffing are under 2200 rpm rotating speeds, to stir 0.8 hour; The vinyl resin of said adding, silicone resin, nano modifier are under 1400 rpm rotating speeds, to stir 0.5 hour.

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